EP0220614B1 - Direct hair dyeing composition containing derivatives of nitrodiphenyl amine - Google Patents

Direct hair dyeing composition containing derivatives of nitrodiphenyl amine Download PDF

Info

Publication number
EP0220614B1
EP0220614B1 EP86114302A EP86114302A EP0220614B1 EP 0220614 B1 EP0220614 B1 EP 0220614B1 EP 86114302 A EP86114302 A EP 86114302A EP 86114302 A EP86114302 A EP 86114302A EP 0220614 B1 EP0220614 B1 EP 0220614B1
Authority
EP
European Patent Office
Prior art keywords
hair
group
dyes
phenylenediamine
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP86114302A
Other languages
German (de)
French (fr)
Other versions
EP0220614A1 (en
Inventor
David Dr. Rose
Edgar Lieske
Norbert Dr. Maak
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT86114302T priority Critical patent/ATE60221T1/en
Publication of EP0220614A1 publication Critical patent/EP0220614A1/en
Application granted granted Critical
Publication of EP0220614B1 publication Critical patent/EP0220614B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • A61K8/418—Amines containing nitro groups
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
    • A61Q5/065—Preparations for temporary colouring the hair, e.g. direct dyes

Definitions

  • the invention relates to hair dyes containing direct hair dyes.
  • hair dyes contain substantive hair dyes in a cosmetic carrier.
  • Such hair dyes often contain additional oxidation dye precursors to achieve certain shades.
  • Creams, emulsions, gels, shampoos, foam aerosols or other preparations which are suitable for use on the hair serve as cosmetic carriers for the direct hair dyes and, if appropriate, oxidation dye precursors.
  • the direct hair dyes play an important role in dyeing hair.
  • the direct dyes have the advantage that they are used without the addition of oxidizing agents.
  • Compounds belonging to the group of nitrobenzene derivatives are predominantly used as direct dyes. They are used either alone or in combination with other substantive dyes such as anthraquinone dyes, indophenols, triphenylmethane dyes, cationic azo dyes or with oxidation dyes.
  • direct nitrobenzene derivatives the nitroanilines and their derivatives play a special role, since some of these dyes develop intense colors with good lightfastness.
  • a disadvantage of the known direct nitroaniline dyes is on the one hand a limited water solubility, which leads to problems in the formulation of the hair dye, on the other hand the unsatisfactory fastness to washing, i. H. that the hair color bleed out heavily after repeated washing.
  • Direct dyes are also said to have good compatibility with other dyes, e.g. B. with oxidation dye precursors and with the usual components in oxidation hair dyes, since they like to combine direct dyes and oxidation dyes for the modification of shades. Good stability against reducing agents and against oxidizing agents is therefore necessary.
  • hair dyes which act as substantive hair dyes are compounds of the general formula I in which one of the groups R1 or R2 is a nitro group and the other is an -SO3H or -COOH group, and the groups R3 to R5 independently of one another hydrogen, alkyl groups having 1 to 4 carbon atoms or one of the groups R3 to R5 one Hydroxyl group or an amino group of the formula NR6R7 is in which R6 and R7 are hydrogen, alkyl groups having 1 to 4 carbon atoms or hydroxyalkyl groups having 2 to 4 carbon atoms, and the other two are hydrogen or alkyl groups having 1 to 4 carbon atoms or which is a hydrogen or an alkyl group with 1 to 4 carbon atoms and the other is a hydroxymethyl group, an alkoxy group with 1 to 4 carbon atoms or chlorine, or whose water-soluble salts are contained, meet the requirements to a high degree.
  • the dyes of the general formula I produce yellow to copper-colored shades of high intensity, light and wash fastness on the hair. They also have better solubility in the aqueous alkaline medium compared to known nitroaniline dyes. From a dermatological and toxicological point of view, the compounds of the formula I are harmless and are therefore particularly suitable for use in hair colorants.
  • Another subject of the invention are therefore compounds of formula I in which one of the groups R1 or R2 is a nitro group and the other is an -SO3H or -COOH group and the group R3 is a hydroxyl group or an amino group-NR6R7, in which R6 and R7 Are hydrogen, alkyl groups with 1 to 4 carbon atoms or hydroxyalkyl groups with 2 to 4 carbon atoms and R4 and R5 are hydrogen or alkyl groups with 1 to 4 carbon atoms or one of the groups R4 or R5 is hydrogen or an alkyl group with 1 to 4 C atoms and the other is a hydroxymethyl group, an alkoxy group with 1 to 4 C atoms or chlorine and their water-soluble salts.
  • water-soluble salts are primarily the salts of strong bases such as the alkali salts, e.g. B. the sodium or potassium salt or ammonium salts, alkanolammonium salts with 2 to 4 carbon atoms in the alkanol group such as. B. to understand the monoethanolammonium salt, the triethanolammonium salt or the isopropanolammonium salt.
  • the hair dye according to the invention can the substantive nitrodiphenylamine derivatives of all general formula I alone or in combination with known substantive dyes, for. B. with other nitrobenzene derivatives, anthraquinone, triphenylmethane or azo dyes.
  • the direct dyes of the general formula I are also very suitable for combination with oxidation dye precursors, that is to say for modifying the nuances of oxidation hair dyeing agents.
  • Oxidation hair colorants contain, as dye precursors, developer components which form the oxidation dyes by oxidative coupling with one another or with suitable coupler components.
  • developer substances such.
  • M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are used as coupler substances.
  • the substantive hair dyes and, if appropriate, the oxidation dye precursors are in a suitable cosmetic carrier, for. B. in creams, emulsions, gels or surfactant-containing, foaming solutions, for. B. incorporated in shampoos, foam aerosols or other preparations that are suitable for use on the hair.
  • Common components of such cosmetic preparations are e.g. B. wetting and emulsifying agents such as anionic, nonionic or ampholytic surfactants, e.g. B. fatty alcohol sulfates, alkane sulfonates, alpha-olefin sulfonates, fatty alcohol polyglycol ether sulfates, ethylene oxide addition products to fatty alcohols, fatty acids and alkylphenols, sorbitan fatty acid esters and fatty acid partial glycerides, Fatty acid alkanolamides and thickeners such as.
  • B. wetting and emulsifying agents such as anionic, nonionic or ampholytic surfactants
  • fatty alcohol sulfates alkane sulfonates, alpha-olefin sulfonates, fatty alcohol polyglycol ether sulfates, ethylene oxide addition products to fatty alcohols, fatty acids and alkylphenols, sorbitan
  • methyl or hydroxyethyl cellulose starch, fatty alcohols, paraffin oils, fatty acids, also perfume oils and hair care additives, such as.
  • the constituents of the cosmetic carriers are used to produce the hair colorants according to the invention in amounts customary for these purposes; e.g. For example, emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant.
  • the substantive hair dyes of the general formula I are used in the hair colorants according to the invention in an amount of 0.01 to 5.0% by weight, preferably 0.1 to 2% by weight, based on the total hair colorant.
  • known oxidation hair dye precursors can be present in an amount of 0.01 to 5, preferably 1 to 3,% by weight.
  • the hair dye according to the invention contains oxidation dye precursors, the addition of a small amount of a reducing agent, e.g. B. from 0.5 to 2.0 wt .-% sodium sulfite to stabilize the oxidation dye precursors.
  • a reducing agent e.g. B. from 0.5 to 2.0 wt .-% sodium sulfite
  • an oxidizing agent is added to the hair dye in order to initiate the oxidative development of the oxidation dye precursors.
  • Particularly suitable oxidizing agents are hydrogen peroxide or its adducts with urea, melamine or sodium borate and mixtures of such hydrogen peroxide adducts with potassium peroxide sulfate.
  • the hair colorants according to the invention regardless of the type of cosmetic preparation, for example as a cream, gel or shampoo, in weakly acidic, neutral or alkaline environment.
  • the hair colorants are preferably used in a pH range from 8 to 10.
  • the application temperatures can be in a range between 15 ° C. and 40 ° C.
  • the hair dye is rinsed away from the hair to be colored.
  • the hair is then washed with a mild shampoo and dried. Washing with a shampoo is not necessary if a carrier with a high surfactant content, e.g. B. a coloring shampoo was used.
  • hair colorations of high intensity and good fastness properties in particular also of good wash fastness and high stability against bleeding and color changes during shampooing, can be achieved.
  • the following examples are intended to explain the subject of the invention in more detail, but without restricting it thereto.
  • Example 14 The preparation was carried out as in Example 14. Instead of p-phenylenediamine, 4.4 g of p-toluenediamine sulfate (0.02 mol) were used. Light brown crystals. Melting point 188 ° C (with decomposition)
  • the ingredients were mixed together in order. After the direct dyes had been added, the pH of the emulsion was adjusted to 9.5 with concentrated ammonia solution, and the mixture was then made up to 100 g with water.
  • the coloring cream was applied to approx. 5 cm long strands of standardized, 90% gray, but not specially pretreated human hair and left there at 27 ° C for 30 minutes. After the dyeing process was completed, the hair was rinsed, washed out with a customary shampoo and then dried.
  • the compounds according to Examples 1 to 26 were used as direct hair dyes.

Abstract

Novel substituted nitrodiphenylamines and substantive hair dye preparations containing them or containing nitrodiphenylamines with different substituents. The dyes result in yellow to copper-colored shades of high intensity and fastness and are more soluble in water than known nitroanilines dyes.

Description

Gegenstand der Erfindung sind Haarfärbemittel mit einem Gehalt an direktziehenden Haarfarbstoffen. Solche Haarfärbemittel ent­halten direktziehende Haarfarbstoffe in einem kosmetischen Träger. Oft enthalten solche Haarfärbemittel zur Erzielung be­stimmter Nuancen zusätzlich Oxidationsfarbstoffvorprodukte. Als kosmetische Träger für die direktziehenden Haarfarbstoffe und gegebenenfalls Oxidationsfarbstoffvorprodukte dienen Cremes, Emulsionen, Gele, Shampoos, Schaumaerosole oder andere Zube­reitungen, die für die Anwendung auf dem Haar geeignet sind.The invention relates to hair dyes containing direct hair dyes. Such hair dyes contain substantive hair dyes in a cosmetic carrier. Such hair dyes often contain additional oxidation dye precursors to achieve certain shades. Creams, emulsions, gels, shampoos, foam aerosols or other preparations which are suitable for use on the hair serve as cosmetic carriers for the direct hair dyes and, if appropriate, oxidation dye precursors.

Für das Färben von Haar spielen neben den Oxidationsfarben, die durch oxidative Kupplung einer oder mehrerer Entwicklerkompo­nenten untereinander oder mit einer oder mehreren Kupplerkom­ponenten entstehen, besonders die direktziehenden Haarfarbstoffe eine wichtige Rolle. Die direktziehenden Farbstoffe haben den Vorteil, daß sie ohne Zusatz von Oxidationsmitteln zur Anwendung kommen. Als direktziehende Farbstoffe werden vorwiegend Verbin­dungen eingesetzt, die zur Gruppe der Nitrobenzolderivate ge­hören. Sie werden entweder allein oder in Kombination mit an­deren direktziehenden Farbstoffen wie Anthrachinonfarbstoffen, Indophenolen, Triphenylmethanfarbstoffen, kationischen Azofarb­stoffen oder mit Oxidationsfarbstoffen eingesetzt.In addition to the oxidation colors that result from the oxidative coupling of one or more developer components with one another or with one or more coupler components, the direct hair dyes play an important role in dyeing hair. The direct dyes have the advantage that they are used without the addition of oxidizing agents. Compounds belonging to the group of nitrobenzene derivatives are predominantly used as direct dyes. They are used either alone or in combination with other substantive dyes such as anthraquinone dyes, indophenols, triphenylmethane dyes, cationic azo dyes or with oxidation dyes.

Gute Haarfärbemittel müssen die gewünschten Farbnuancen in aus­reichender Intensität ausbilden. Sie müssen ein gutes Aufzieh­vermögen auf menschlichem Haar besitzen, ohne die Kopfhaut zu stark anzufärben. Die damit erzeugten Färbungen müssen eine hohe Stabilität gegen Licht, Wärme, Schweiß, Haarwaschmittel und die bei der Dauerwellung des Haares verwendeten Chemikalien aufweisen. Sie sollen schließlich in toxikologischer und dermato­logischer Hinsicht unbedenklich sein.Good hair dyes must develop the desired color shades in sufficient intensity. You need to have good absorbency on human hair without staining the scalp too much. The colorations generated with it must be one have high stability against light, heat, sweat, shampoo and the chemicals used in permanent hair waving. After all, they should be harmless from a toxicological and dermatological point of view.

Unter den direktziehenden Nitrobenzolderivaten spielen die Ni­troaniline und deren Derivate eine besondere Rolle, da einige dieser Farbstoffe intensive Färbungen von guter Lichtechtheit ausbilden. Ein Nachteil der bekannten direktziehenden Nitro­anilin-Farbstoffe ist jedoch einerseits eine begrenzte Wasser­löslichkeit, die zu Problemen bei der Formulierung der Haar­färbemittel führt, andererseits die unbefriedigende Waschechtheit, d. h. daß die Haarfärbungen nach mehrmaligem Haarwaschen stark ausbluten. Direktziehende Farbstoffe sollen darüber hinaus eine gute Verträglichkeit mit anderen Farbstoffen, z. B. mit Oxidationsfarbstoffvorprodukten und mit den in Oxidationshaar­färbemitteln üblichen Komponenten aufweisen, da man zur Nuan­cenabwandlung gerne direktziehende Farbstoffe und Oxidations­farbstoffe kombiniert. Daher ist eine gute Stabilität gegen Re­duktionsmittel und gegen Oxidationsmittel erforderlich.Among the direct nitrobenzene derivatives, the nitroanilines and their derivatives play a special role, since some of these dyes develop intense colors with good lightfastness. A disadvantage of the known direct nitroaniline dyes, however, is on the one hand a limited water solubility, which leads to problems in the formulation of the hair dye, on the other hand the unsatisfactory fastness to washing, i. H. that the hair color bleed out heavily after repeated washing. Direct dyes are also said to have good compatibility with other dyes, e.g. B. with oxidation dye precursors and with the usual components in oxidation hair dyes, since they like to combine direct dyes and oxidation dyes for the modification of shades. Good stability against reducing agents and against oxidizing agents is therefore necessary.

Es wurde gefunden, daß Haarfärbemittel, die als direktziehende Haarfarbstoffe Verbindungen der allgemeinen Formel I

Figure imgb0001

in der eine der Gruppen R¹ oder R² eine Nitrogruppe und die andere eine -SO₃H oder -COOH-Gruppe ist, und die Gruppen R³ bis R⁵ unabhängig voneinander Wasserstoff, Alkylgruppen mit 1 bis 4 C-Atomen oder eine der Gruppen R³ bis R⁵ eine Hydroxylgruppe oder eine Aminogruppe der Formel NR⁶R⁷ ist, in der R⁶ und R⁷ Wasserstoff, Alkylgruppen mit 1 bis 4 C-Atomen oder Hydroxyalkylgruppen mit 2 bis 4 C-Atomen sind, und die beiden anderen Wasserstoff oder Alkylgruppen mit 1 bis 4 C-Atomen oder die eine Wasserstoff oder eine Alkylgruppe mit 1 bis 4 C-Atomen und die andere eine Hydroxymethylgruppe, eine Alkoxygruppe mit 1 bis 4 C-Atomen oder Chlor ist, oder deren wasserlösliche Salze enthalten sind, die gestellten Anforderungen in hohem Maße erfüllen.It has been found that hair dyes which act as substantive hair dyes are compounds of the general formula I
Figure imgb0001
in which one of the groups R¹ or R² is a nitro group and the other is an -SO₃H or -COOH group, and the groups R³ to R⁵ independently of one another hydrogen, alkyl groups having 1 to 4 carbon atoms or one of the groups R³ to R⁵ one Hydroxyl group or an amino group of the formula NR⁶R⁷ is in which R⁶ and R⁷ are hydrogen, alkyl groups having 1 to 4 carbon atoms or hydroxyalkyl groups having 2 to 4 carbon atoms, and the other two are hydrogen or alkyl groups having 1 to 4 carbon atoms or which is a hydrogen or an alkyl group with 1 to 4 carbon atoms and the other is a hydroxymethyl group, an alkoxy group with 1 to 4 carbon atoms or chlorine, or whose water-soluble salts are contained, meet the requirements to a high degree.

Die Farbstoffe der allgemeinen Formel I erzeugen auf dem Haar gelbe bis kupferfarbige Nuancen von hoher Intensität, Licht- und Waschechtheit. Sie besitzen darüber hinaus im Vergleich zu be­kannten Nitroanilinfarbstoffen eine bessere Löslichkeit im wäßrig-alkalischen Medium. In dermatologischer und toxikolo­gischer Hinsicht sind die Verbindungen der Formel I unschädlich und daher für die Anwendung in Haarfärbemitteln besonders ge­eignet.The dyes of the general formula I produce yellow to copper-colored shades of high intensity, light and wash fastness on the hair. They also have better solubility in the aqueous alkaline medium compared to known nitroaniline dyes. From a dermatological and toxicological point of view, the compounds of the formula I are harmless and are therefore particularly suitable for use in hair colorants.

Verbindungen der allgemeinen Formel I, in der R³, R⁴ und R⁵ Wasserstoff ist, sind literaturbekannt. Die Herstellung der übrigen Verbindungen der allgemeinen Formel I erfolgt allgemein durch Umsetzung eines 1-Chlor-2-nitrobenzolderivats der For­mel II

Figure imgb0002
mit einem Anilinderivat der Formel III
Figure imgb0003
unter Abspaltung von HCl in Gegenwart einer Base.Compounds of the general formula I in which R³, R⁴ and R⁵ is hydrogen are known from the literature. The other compounds of the general formula I are generally prepared by reacting a 1-chloro-2-nitrobenzene derivative of the formula II
Figure imgb0002
 with an aniline derivative of formula III
Figure imgb0003
with the elimination of HCl in the presence of a base.

Dabei haben die Gruppen R¹ bis R⁵ die für die Formel I ange­gebene Bedeutung.The groups R¹ to R⁵ have the meaning given for the formula I.

Verbindungen der Formel I, in der die Gruppe R³ eine Hydroxyl­gruppe oder eine Aminogruppe -NR⁶R⁷, wobei R⁶ und R⁷ die vor­genannte Bedeutung haben, sind besonders geeignet und nicht literaturbekannt.Compounds of the formula I in which the group R³ is a hydroxyl group or an amino group -NR⁶R⁷, where R⁶ and R⁷ have the abovementioned meaning, are particularly suitable and are not known from the literature.

Ein weiterer Erfindungsgegenstand sind daher Verbindungen der Formel I, in der eine der Gruppen R¹ oder R² eine Nitrogruppe und die andere eine -SO₃H oder -COOH-Gruppe ist und die Grup­pe R³ eine Hydroxylgruppe oder eine Aminogruppe-NR⁶R⁷ ist, in der R⁶ und R⁷ Wasserstoff, Alkylgruppen mit 1 bis 4 C-Atomen oder Hydroxyalkylgruppen mit 2 bis 4 C-Atomen sind und R⁴ und R⁵ Wasserstoff oder Alkylgruppen mit 1 bis 4 C-Atomen sind oder eine der Gruppen R⁴ oder R⁵ Wasserstoff oder eine Alkylgruppe mit 1 bis 4 C-Atomen und die andere eine Hydroxymethylgruppe, eine Alkoxygruppe mit 1 bis 4 C-Atomen oder Chlor ist und deren wasserlösliche Salze.Another subject of the invention are therefore compounds of formula I in which one of the groups R¹ or R² is a nitro group and the other is an -SO₃H or -COOH group and the group R³ is a hydroxyl group or an amino group-NR⁶R⁷, in which R⁶ and R⁷ Are hydrogen, alkyl groups with 1 to 4 carbon atoms or hydroxyalkyl groups with 2 to 4 carbon atoms and R⁴ and R⁵ are hydrogen or alkyl groups with 1 to 4 carbon atoms or one of the groups R⁴ or R⁵ is hydrogen or an alkyl group with 1 to 4 C atoms and the other is a hydroxymethyl group, an alkoxy group with 1 to 4 C atoms or chlorine and their water-soluble salts.

Unter wasserlöslichen Salzen sind in erster Linie die Salze starker Basen wie etwa die Alkalisalze, z. B. das Natrium- oder Kalium­salz oder Ammoniumsalze, Alkanolammoniumsalze mit 2 bis 4 C-Atomen in der Alkanolgruppe wie z. B. das Monoethanolammo­niumsalz, das Triethanolammoniumsalz oder das Isopropanolam­moniumsalz zu verstehen. Die erfindungsgemäßen Haarfärbemittel können die direktziehenden Nitrodiphenylaminderivate der all­ gemeinen Formel I allein oder in Kombination mit bekannten direktziehenden Farbstoffen, z. B. mit anderen Nitrobenzolderi­vaten, Anthrachinonfarbstoffen, Triphenylmethan- oder Azofarb­stoffen enthalten. Darüber hinaus eignen sich die direktziehenden Farbstoffe der allgemeinen Formel I wegen ihrer hohen Bestän­digkeit gegenüber Reduktionsmitteln und Oxidationsmitteln auch sehr gut zur Kombination mit Oxidationsfarbstoffvorprodukten, also zur Modifikation der Nuancen von Oxidationshaarfärbemitteln. Oxidationshaarfärbemittel enthalten als Farbstoffvorprodukte Entwicklerkomponenten, die durch oxidative Kupplung untereinan­der oder mit geeigneten Kupplerkomponenten die Oxidationsfarb­stoffe ausbilden. Als Entwicklersubstanzen werden z. B. primäre aromatische Amine mit einer weiteren, in Para- oder Orthoposition befindlichen freien oder substituierten Hydroxy- oder Amino­gruppe, Diaminopyridinderivate, heterocyclische Hydrazone, 4-Aminopyrazolonderivate und 2,4,5,6-Tetraaminopyrimidin und dessen Derivate eingesetzt. Als Kupplersubstanzen werden m-Phe­nylendiaminderivate, Naphthole, Resorcin und Resorcinderivate, Pyrazolone und m-Aminophenole verwendet.Among water-soluble salts are primarily the salts of strong bases such as the alkali salts, e.g. B. the sodium or potassium salt or ammonium salts, alkanolammonium salts with 2 to 4 carbon atoms in the alkanol group such as. B. to understand the monoethanolammonium salt, the triethanolammonium salt or the isopropanolammonium salt. The hair dye according to the invention can the substantive nitrodiphenylamine derivatives of all general formula I alone or in combination with known substantive dyes, for. B. with other nitrobenzene derivatives, anthraquinone, triphenylmethane or azo dyes. In addition, because of their high resistance to reducing agents and oxidizing agents, the direct dyes of the general formula I are also very suitable for combination with oxidation dye precursors, that is to say for modifying the nuances of oxidation hair dyeing agents. Oxidation hair colorants contain, as dye precursors, developer components which form the oxidation dyes by oxidative coupling with one another or with suitable coupler components. As developer substances such. B. primary aromatic amines with a further, in para or ortho position free or substituted hydroxy or amino group, diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazolone derivatives and 2,4,5,6-tetraaminopyrimidine and its derivatives. M-Phenylenediamine derivatives, naphthols, resorcinol and resorcinol derivatives, pyrazolones and m-aminophenols are used as coupler substances.

Zur Herstellung der erfindungsgemäßen Haarfärbemittel werden die direktziehenden Haarfarbstoffe und gegebenenfalls die Oxi­dationsfarbstoffvorprodukte in einen geeigneten kosmetischen Träger, z. B. in Cremes, Emulsionen, Gele oder auch tensidhal­tige, schäumende Lösungen, z. B. in Shampoos, Schaumaerosole oder andere Zubereitungen eingearbeitet, die für die Anwendung auf dem Haar geeignet sind.To produce the hair colorants according to the invention, the substantive hair dyes and, if appropriate, the oxidation dye precursors are in a suitable cosmetic carrier, for. B. in creams, emulsions, gels or surfactant-containing, foaming solutions, for. B. incorporated in shampoos, foam aerosols or other preparations that are suitable for use on the hair.

Übliche Bestandteile solcher kosmetischer Zubereitungen sind z. B. Netz- und Emulgiermittel wie anionische, nichtionische oder ampholytische Tenside, z. B. Fettalkoholsulfate, Alkansulfonate, alpha-Olefinsulfonate, Fettalkoholpolyglykolethersulfate, Ethy­lenoxidanlagerungsprodukte an Fettalkohole, Fettsäuren und Al­kylphenole, Sorbitanfettsäureester und Fettsäurepartialglyceride, Fettsäurealkanolamide sowie Verdickungsmittel wie z. B. Methyl-­oder Hydroxyethylcellulose, Stärke, Fettalkohole, Paraffinöle, Fettsäuren, ferner Parfümöle und haarpflegende Zusäzte, wie z. B. wasserlösliche kationische Polymere, Proteinderivate, Pantothensäure und Cholesterin. Die Bestandteile der kosme­tischen Träger werden zur Herstellung der erfindungsgemäßen Haarfärbemittel in für diese Zwecke üblichen Mengen eingesetzt; z. B. werden Emulgiermittel in Konzentrationen von 0,5 bis 30 Gew.-% und Verdickungsmittel in Konzentrationen von 0,1 bis 25 Gew.-% des gesamten Färbemittels eingesetzt.Common components of such cosmetic preparations are e.g. B. wetting and emulsifying agents such as anionic, nonionic or ampholytic surfactants, e.g. B. fatty alcohol sulfates, alkane sulfonates, alpha-olefin sulfonates, fatty alcohol polyglycol ether sulfates, ethylene oxide addition products to fatty alcohols, fatty acids and alkylphenols, sorbitan fatty acid esters and fatty acid partial glycerides, Fatty acid alkanolamides and thickeners such as. As methyl or hydroxyethyl cellulose, starch, fatty alcohols, paraffin oils, fatty acids, also perfume oils and hair care additives, such as. B. water-soluble cationic polymers, protein derivatives, pantothenic acid and cholesterol. The constituents of the cosmetic carriers are used to produce the hair colorants according to the invention in amounts customary for these purposes; e.g. For example, emulsifiers are used in concentrations of 0.5 to 30% by weight and thickeners in concentrations of 0.1 to 25% by weight of the total colorant.

In den erfindungsgemäßen Haarfärbemitteln werden die direktzie­henden Haarfarbstoffe der allgemeinen Formel I in einer Menge von 0,01 bis 5,0 Gew.-%, bevorzugt von 0,1 bis 2 Gew.-%, bezo­gen auf das gesamte Haarfärbemittel, eingesetzt. Daneben können bekannte Oxidationshaarfärbemittelvorprodukte (Entwickler- und Kupplersubstanzen) in einer Menge von 0,01 bis 5, vorzugsweise von 1 bis 3 Gew.-% enthalten sein.The substantive hair dyes of the general formula I are used in the hair colorants according to the invention in an amount of 0.01 to 5.0% by weight, preferably 0.1 to 2% by weight, based on the total hair colorant. In addition, known oxidation hair dye precursors (developer and coupler substances) can be present in an amount of 0.01 to 5, preferably 1 to 3,% by weight.

Wenn das erfindungsgemäße Haarfärbemittel Oxidationsfarbstoff­vorprodukte enthält, empfiehlt sich außerdem die Zugabe einer kleinen Menge eines Reduktionsmittels, z. B. von 0,5 bis 2,0 Gew.-% Natriumsulfit zur Stabilisierung der Oxidationsfarb­stoffvorprodukte. In diesem Falle wird vor der Anwendung des Haarfärbemittels dieses mit einem Oxidationsmittel versetzt, um die oxidative Entwicklung der Oxidationsfarbstoffvorprodukte einzu­leiten. Als Oxidationsmittel kommen insbesondere Wasserstoff­peroxid oder dessen Anlagerungsprodukte an Harnstoff, Melamin oder Natriumborat sowie Gemische aus derartigen Wasserstoff­peroxidanlagerungsprodukten mit Kaliumperoxidsulfat in Frage.If the hair dye according to the invention contains oxidation dye precursors, the addition of a small amount of a reducing agent, e.g. B. from 0.5 to 2.0 wt .-% sodium sulfite to stabilize the oxidation dye precursors. In this case, an oxidizing agent is added to the hair dye in order to initiate the oxidative development of the oxidation dye precursors. Particularly suitable oxidizing agents are hydrogen peroxide or its adducts with urea, melamine or sodium borate and mixtures of such hydrogen peroxide adducts with potassium peroxide sulfate.

Die Anwendung der erfindungsgemäßen Haarfärbemittel kann, un­abhängig von der Art der kosmetischen Zubereitung, zum Beispiel als Creme, Gel oder Shampoo, im schwach sauren, neutralen oder alkalischen Milieu erfolgen. Bevorzugt ist die Anwendung der Haarfärbemittel in einem pH-Bereich von 8 bis 10. Die Anwen­dungstemperaturen können in einem Bereich zwischen 15°C und 40°C liegen. Nach einer Einwirkungszeit von ca. 30 Minuten wird das Haarfärbemittel durch Ausspülen von dem zu färbenden Haar entfernt. Danach wird das Haar mit einem milden Shampoo nach­gewaschen und getrocknet. Das Nachwaschen mit einem Shampoo entfällt, wenn ein stark tensidhaltiger Träger, z. B. ein Fär­beshampoo, verwendet wurde.The use of the hair colorants according to the invention, regardless of the type of cosmetic preparation, for example as a cream, gel or shampoo, in weakly acidic, neutral or alkaline environment. The hair colorants are preferably used in a pH range from 8 to 10. The application temperatures can be in a range between 15 ° C. and 40 ° C. After an exposure time of approx. 30 minutes, the hair dye is rinsed away from the hair to be colored. The hair is then washed with a mild shampoo and dried. Washing with a shampoo is not necessary if a carrier with a high surfactant content, e.g. B. a coloring shampoo was used.

Mit den erfindungsgemäßen Haarfärbemitteln lassen sich Haaran­färbungen von hoher Intensität und guten Echtheitseigenschaften, besonders auch von guter Waschechtheit und hoher Stabilität ge­gen Ausbluten und Farbveränderungen beim Shamponieren erzie­len. Die nachfolgenden Beispiele sollen den Erfindungsgegenstand näher erläutern, ohne ihn jedoch hierauf zu beschränken.With the hair colorants according to the invention, hair colorations of high intensity and good fastness properties, in particular also of good wash fastness and high stability against bleeding and color changes during shampooing, can be achieved. The following examples are intended to explain the subject of the invention in more detail, but without restricting it thereto.

BeispieleExamples HerstellungsbeispieleManufacturing examples 1. 2,6-Dinitro-4ʹ-dimethylamino-diphenylamin-4-sulfonsäure-K-­Salz 1. 2,6-dinitro-4ʹ-dimethylamino-diphenylamine-4-sulfonic acid K salt

Eine Mischung aus 5 g 4-Chlor-3,5-dinitrobenzolsulfon­säure-K-Salz (0,016 Mol), 2,2 g N,N-Dimethyl-p-phenylen­diamin (0,016 Mol) und 1,1 g Kaliumcarbonat (0,008 Mol) in 50 ml Wasser wurde 1 Stunde unter Rückfluß gekocht. Nach dem Abkühlen wurde der Niederschlag abfiltriert. Es wurde ein ockerbraunes Pulver erhalten.
UV-Spektrum (pH = 9,5) λMAX = 437 nmA mixture of 5 g of 4-chloro-3,5-dinitrobenzenesulfonic acid K salt (0.016 mol), 2.2 g of N, N-dimethyl-p-phenylenediamine (0.016 mol) and 1.1 g of potassium carbonate (0.008 mol) in 50 ml of water was refluxed for 1 hour. After cooling, the precipitate was filtered off. An ocher powder was obtained.
UV spectrum (pH = 9.5) λ MAX = 437 nm

2. 2,6-Dinitro-4ʹ-amino-diphenylamin-4-sulfonsäure-K-Salz 2. 2,6-Dinitro-4ʹ-amino-diphenylamine-4-sulfonic acid K salt

Die Herstellung erfolgte analog Beispiel 1. Anstatt N,N-Di­methyl-p-phenylendiamin wurden 1,73 g p-Phenylendiamin (0,016 Mol) eingesetzt.
UV-Spektrum (pH = 9,5) λMAX = 431 nmThe preparation was carried out analogously to Example 1. Instead of N, N-dimethyl-p-phenylenediamine, 1.73 g of p-phenylenediamine (0.016 mol) were used.
UV spectrum (pH = 9.5) λ MAX = 431 nm

3. 2,6-Dinitro-4ʹ-methylamino-diphenylamin-4-sulfonsäure-K-Salz 3. 2,6-dinitro-4ʹ-methylamino-diphenylamine-4-sulfonic acid K salt

Die Herstellung erfolgte analog Beispiel 1. Anstatt N,N-Di­methyl-p-phenylendiamin wurden 3,1 g N-Methyl-p-phenylen­diamin (0,016 Mol) eingesetzt.
UV-Spektrum (pH = 9,5) λMAX = 441 nmThe preparation was carried out analogously to Example 1. Instead of N, N-dimethyl-p-phenylenediamine, 3.1 g of N-methyl-p-phenylenediamine (0.016 mol) were used.
UV spectrum (pH = 9.5) λ MAX = 441 nm

4. 2,6-Dinitro-2ʹ-methyl-4ʹ-amino-diphenylamin-4-sulfonsäure-­K-Salz 4. 2,6-dinitro-2ʹ-methyl-4ʹ-amino-diphenylamine-4-sulfonic acid K salt

Die Herstellung erfolgte analog Beispiel 1. Anstatt N,N-Di­methyl-p-phenylendiamin wurden 3,5 g p-Toluylendiaminsulfat (0,016 Mol) eingesetzt. Rotbraunes Pulver.
UV-Spektrum (pH = 9,5) λMAX = 449 nmThe preparation was carried out analogously to Example 1. Instead of N, N-dimethyl-p-phenylenediamine, 3.5 g of p-toluenediamine sulfate (0.016 mol) were used. Red-brown powder.
UV spectrum (pH = 9.5) λ MAX = 449 nm

5. 2,6-Dinitro-4ʹ-N,N-bis-(β-hydroxyethyl)-amino-diphenylamin-­4-sulfonsäure-K-Salz 5. 2,6-dinitro-4ʹ-N, N-bis- (β-hydroxyethyl) amino-diphenylamine-4-sulfonic acid K salt

Die Herstellung erfolgte analog Beispiel 1. Anstatt N,N-Di­methyl-p-phenylendiamin wurden 5,2 g N,N-Bis-(β-hydroxy­ethyl)-p-phenylendiamin (0,016 Mol) eingesetzt. Rotbraunes Pulver.
UV-Spektrum (pH = 9,5) λMAX = 443 nmThe preparation was carried out analogously to Example 1. Instead of N, N-dimethyl-p-phenylenediamine, 5.2 g of N, N-bis- (β-hydroxyethyl) -p-phenylenediamine (0.016 mol) were used. Red-brown powder.
UV spectrum (pH = 9.5) λ MAX = 443 nm

6. 2,6-Dinitro-2ʹ-chlor-4ʹ-amino-diphenylamin-4-sulfonsäure-­K-Salz 6. 2,6-Dinitro-2ʹ-chloro-4ʹ-amino-diphenylamine-4-sulfonic acid K salt

Die Herstellung erfolgte analog Beispiel 1. Anstatt N,N-Di­methyl-p-phenylendiamin wurden 3,85 g 2-Chlor-p-phenylen-­diaminsulfat (0,016 Mol) eingesetzt. Rotbraune Kristalle.
IR-Spektrum (KBr; cm⁻¹); 1620, 1565, 1530, 1505, 1420, 1340, 1270, 1240, 1205, 1150, 1130, 1110, 1045, 920, 910, 895, 825The preparation was carried out analogously to Example 1. Instead of N, N-dimethyl-p-phenylene diamine, 3.85 g of 2-chloro-p-phenylene diamine sulfate (0.016 mol) were used. Red-brown crystals.
IR spectrum (KBr; cm⁻¹); 1620, 1565, 1530, 1505, 1420, 1340, 1270, 1240, 1205, 1150, 1130, 1110, 1045, 920, 910, 895, 825

7. 2,6-Dinitro-2ʹ,3ʹ-dimethyl-4ʹ-amino-diphenylamin-4-sulfon­säure-K-Salz 7. 2,6-dinitro-2ʹ, 3ʹ-dimethyl-4ʹ-amino-diphenylamine-4-sulfonic acid K salt

Die Herstellung erfolgte analog Beispiel 1. Anstatt N,N-Di­methyl-p-phenylendiamin wurden 2,2 g (0,016 Mol) 2,3-Di­methyl-p-phenylendiamin eingesetzt. Braune Kristalle.
IR-Spektrum (KBr; cm⁻¹); 1620, 1565, 1530, 1490, 1420, 1345, 1270, 1210, 1180, 1105, 1050, 930, 905, 835, 820The preparation was carried out analogously to Example 1. Instead of N, N-dimethyl-p-phenylenediamine, 2.2 g (0.016 mol) of 2,3-dimethyl-p-phenylenediamine were used. Brown crystals.
IR spectrum (KBr; cm⁻¹); 1620, 1565, 1530, 1490, 1420, 1345, 1270, 1210, 1180, 1105, 1050, 930, 905, 835, 820

8. 2,6-Dinitro-3ʹ-hydroxymethyl-4ʹ-amino-diphenylamin-4-sulfon­säure-K-Salz 8. 2,6-Dinitro-3ʹ-hydroxymethyl-4ʹ-amino-diphenylamine-4-sulfonic acid K salt

Die Herstellung erfolgte analog Beispiel 1. Anstatt N,N-Di­methyl-p-phenylendiamin wurden 3,8 g 2,5-Diaminobenzyl­alkohol (0,016 Mol) eingesetzt. Braune Kristalle.
UV-Spektrum (pH = 9,5) λMAX = 427 nmThe preparation was carried out analogously to Example 1. Instead of N, N-dimethyl-p-phenylenediamine, 3.8 g of 2,5-diaminobenzyl alcohol (0.016 mol) were used. Brown crystals.
UV spectrum (pH = 9.5) λ MAX = 427 nm

9. 2,6-Dinitro-2ʹ-methoxy-4ʹamino-diphenylamin-4-sulfonsäure-K-­Salz 9. 2,6-dinitro-2ʹ-methoxy-4ʹamino-diphenylamine-4-sulfonic acid K salt

Die Herstellung erfolgte analog Beispiel 1. Anstatt N,N-Di­methyl-p-phenylendiamin wurden 3,8 g 2,5-Diaminoanisolsul­fat (0,016 Mol) eingesetzt. Braune Kristalle.
UV-Spektrum (pH = 9,5) λMAX = 424 nmThe preparation was carried out analogously to Example 1. Instead of N, N-dimethyl-p-phenylenediamine, 3.8 g of 2,5-diamino anisole sulfate (0.016 mol) were used. Brown crystals.
UV spectrum (pH = 9.5) λ MAX = 424 nm

10. 2,6-Dinitro-4ʹ-hydroxy-diphenylamin-4-sulfonsäure-K-Salz 10. 2,6-Dinitro-4ʹ-hydroxy-diphenylamine-4-sulfonic acid K salt

Die Herstellung erfolgte analog Beispiel 1. Anstatt N,N-Di­methyl-p-phenylendiamin wurden 1,75 g p-Aminophenol (0,016 Mol) eingesetzt.The preparation was carried out analogously to Example 1. Instead of N, N-dimethyl-p-phenylenediamine, 1.75 g of p-aminophenol (0.016 mol) were used.

11. 2,6-Dinitro-4ʹ-N-ethyl-N-β-hydroxyethylamino-diphenylamin-­4-sulfonsäure-K-Salz 11. 2,6-Dinitro-4ʹ-N-ethyl-N-β-hydroxyethylamino-diphenylamine-4-sulfonic acid K salt

Die Herstellung erfolgte analog Beispiel 1. Anstatt N,N-Di­methyl-p-phenylendiamin wurden 4,5 g N-Ethyl-N-β-hy­droxyethyl-p-phenylendiaminsulfat eingesetzt. Schwarze Kristalle.
UV-Spektrum (pH = 9,5) λMAX = 446 nmThe preparation was carried out analogously to Example 1. Instead of N, N-dimethyl-p-phenylenediamine, 4.5 g of N-ethyl-N-β-hydroxyethyl-p-phenylenediamine sulfate were used. Black crystals.
UV spectrum (pH = 9.5) λ MAX = 446 nm

12. 2,6-Dinitro-2ʹ-methyl-4ʹ-N,N-diethylamino-diphenylamin-4-sul­fonsäure-K-Salz 12. 2,6-Dinitro-2ʹ-methyl-4ʹ-N, N-diethylamino-diphenylamine-4-sulfonic acid K salt

Die Herstellung erfolgte analog Beispiel 1. Anstatt N,N-Di­methyl-p-phenylendiamin wurden 3,4 g N,N-Diethyl-2-methyl-­p-phenylendiamin-dihydrochlorid (0,016 Mol) eingesetzt. Schwarze Kristalle.
IR-Spektrum (KBr; cm⁻¹); 1620, 1565, 1510, 1470, 1450, 1430, 1400, 1380, 1355, 1340, 1265, 1240, 1200, 1115, 1100, 1080, 1045, 930, 905, 870, 840.The preparation was carried out analogously to Example 1. Instead of N, N-dimethyl-p-phenylenediamine, 3.4 g of N, N-diethyl-2-methyl-p-phenylenediamine dihydrochloride (0.016 mol) were used. Black crystals.
IR spectrum (KBr; cm⁻¹); 1620, 1565, 1510, 1470, 1450, 1430, 1400, 1380, 1355, 1340, 1265, 1240, 1200, 1115, 1100, 1080, 1045, 930, 905, 870, 840.

13. 2,4-Dinitro-4ʹ-dimethylamino-diphenylamin-4-carbonsäure 13. 2,4-Dinitro-4ʹ-dimethylamino-diphenylamine-4-carboxylic acid

Eine Mischung bestehend aus 5 g N,N-Dimethyl-p-phenylen­diamin (0,024 Mol), 6 g 3,5-Dinitro-2-chlorbenzoesäure (0,024 Mol) und 3,3 g Kaliumcarbonat in 40 ml Wasser wurde 2 Stunden bei Zimmertemperatur gerührt. Der Niederschlag wurde abfiltriert. Curryfarbene Kristalle.
Schmelzpunkt 249°C (unter Zersetzung)A mixture consisting of 5 g of N, N-dimethyl-p-phenylenediamine (0.024 mol), 6 g of 3,5-dinitro-2-chlorobenzoic acid (0.024 mol) and 3.3 g of potassium carbonate in 40 ml of water were stirred at room temperature for 2 hours. The precipitate was filtered off. Curry colored crystals.
Melting point 249 ° C (with decomposition)

14. 2,6-Dinitro-4ʹ-amino-diphenylamin-4-carbonsäure 14. 2,6-Dinitro-4ʹ-amino-diphenylamine-4-carboxylic acid

Eine Mischung bestehend aus 5 g 4-Chlor-3,5-dinitrobenzoe­säure (0,024 Mol), 3 g p-Phenylendiamin (0,024 Mol) und 5,4 g Natriumacetat, wurde in 60 ml Wasser unter Rückfluß gekocht. Nach dem Abkühlen wurde der Niederschlag abfil­triert und mehrmals mit Wasser ausgekocht. Rückstand: braune Kristalle.
Schmelzpunkt 160°C (unter Zersetzung)A mixture consisting of 5 g of 4-chloro-3,5-dinitrobenzoic acid (0.024 mol), 3 g of p-phenylenediamine (0.024 mol) and 5.4 g of sodium acetate was boiled in 60 ml of water under reflux. After cooling, the precipitate was filtered off and boiled several times with water. Residue: brown crystals.
Melting point 160 ° C (with decomposition)

15. 2,6-Dinitro-4ʹ-amino-3ʹ-methyl-diphenylamin-4-carbonsäure 15. 2,6-Dinitro-4ʹ-amino-3ʹ-methyl-diphenylamine-4-carboxylic acid

Die Herstellung erfolgte analog Beispiel 14. Anstatt p-Phe­nylendiamin wurden 4,4 g p-Toluylendiaminsulfat (0,02 Mol) eingesetzt. Hellbraune Kristalle.
Schmelzpunkt 188°C (unter Zersetzung)The preparation was carried out as in Example 14. Instead of p-phenylenediamine, 4.4 g of p-toluenediamine sulfate (0.02 mol) were used. Light brown crystals.
Melting point 188 ° C (with decomposition)

16. 2,6-Dinitro-4ʹ-N,N-dimethylamino-diphenylamin-4-carbonsäure 16. 2,6-Dinitro-4ʹ-N, N-dimethylamino-diphenylamine-4-carboxylic acid

Die Herstellung erfolgte analog Beispiel 14. Anstatt p-Phe­nylendiamin wurden 5 g N,N-Dimethyl-p-phenylendiamindihy­drochlorid (0,02 Mol) eingesetzt. Schwarze Kristalle.
Schmelzpunkt 228 bis 232°CThe preparation was carried out analogously to Example 14. Instead of p-phenylenediamine, 5 g of N, N-dimethyl-p-phenylenediamine dihydrochloride (0.02 mol) were used. Black crystals.
Melting point 228 to 232 ° C

17. 2,6-Dinitro-4ʹ-hydroxy-diphenylamin-4-carbonsäure 17. 2,6-Dinitro-4ʹ-hydroxy-diphenylamine-4-carboxylic acid

Die Herstellung erfolgte analog Beispiel 14. Anstatt p-Phe­nylendiamin wurden 2,18 g p-Aminophenol (0,02 Mol) einge­setzt. Orangebraune Kristalle.
Schmelzpunkt 240°CThe preparation was carried out analogously to Example 14. Instead of p-phenylenediamine, 2.18 g of p-aminophenol (0.02 mol) were used. Orange-brown crystals.
Melting point 240 ° C

18. 2,4-Dinitro-4ʹ-amino-diphenylamin-6-sulfonsäure-Na-Salz 18. 2,4-Dinitro-4ʹ-amino-diphenylamine-6-sulfonic acid Na salt

Eine Mischung, bestehend aus 10 g 2-chlor-3,5-dinitroben­zolsulfonsäure-Na-Salz (0,034 Mol), 3,7 g p-Phenylendiamin (0,034 Mol) und 2,4 g Kaliumcarbonat (0,017 Mol) in 75 ml Wasser wurde 2 Stunden unter Rückfluß gekocht. Nach dem Abkühlen wurde der Niederschlag abfiltriert. Rotbraune Kristalle.
Schmelzpunkt oberhalb 305°CA mixture consisting of 10 g of 2-chloro-3,5-dinitrobenzenesulfonic acid Na salt (0.034 mol), 3.7 g of p-phenylenediamine (0.034 mol) and 2.4 g of potassium carbonate (0.017 mol) in 75 ml of water was refluxed for 2 hours. After cooling, the precipitate was filtered off. Red-brown crystals.
Melting point above 305 ° C

19. 2,4-Dinitro-2ʹ-chlor-4ʹ-amino-diphenylamin-6-sulfonsäure-Na-­Salz 19. 2,4-Dinitro-2ʹ-chloro-4ʹ-aminodiphenylamine-6-sulfonic acid Na salt

Die Herstellung erfolgte analog Beispiel 18. Anstatt p-Phe­nylendiamin wurden 4,1 g 2-Chlor-p-phenylendiamin (0,017 Mol) eingesetzt. Braune Kristalle.
Schmelzpunkt oberhalb 305°CThe preparation was carried out analogously to Example 18. Instead of p-phenylenediamine, 4.1 g of 2-chloro-p-phenylenediamine (0.017 mol) were used. Brown crystals.
Melting point above 305 ° C

20. 2,4-Dinitro-4ʹ-hydroxy-diphenylamin-6-sulfonsäure-Na-Salz 20. 2,4-Dinitro-4ʹ-hydroxy-diphenylamine-6-sulfonic acid Na salt

Die Herstellung erfolgte analog Beispiel 18. Anstatt p-Phe­nylendiamin wurden 1,86 g p-Aminophenol (0,017 Mol) einge­setzt. Braune Kristalle.
Schmelzpunkt oberhalb 305°CThe preparation was carried out analogously to Example 18. Instead of p-phenylenediamine, 1.86 g of p-aminophenol (0.017 mol) were used. Brown crystals.
Melting point above 305 ° C

21. 2,4-Dinitro-4ʹ-N-ethyl-N-β-hydroxyethyl-aminodiphenylamin-­6-sulfonsäure-Na-Salz 21. 2,4-Dinitro-4ʹ-N-ethyl-N-β-hydroxyethyl-aminodiphenylamine-6-sulfonic acid Na salt

Die Herstellung erfolgte analog Beispiel 18. Anstatt p-Phe­nylendiamin wurden 4,7 g N-Ethyl-N-β-hydroxy-ethyl-p-­phenylendiamin (0,017 Mol) eingesetzt. Schwarze Kristalle.
Schmelzpunkt oberhalb 160°C (unter Zersetzung)The preparation was carried out analogously to Example 18. Instead of p-phenylenediamine, 4.7 g of N-ethyl-N-β-hydroxy-ethyl-p-phenylenediamine (0.017 mol) were used. Black crystals.
Melting point above 160 ° C (with decomposition)

22. 2,4-Dinitro-2ʹ-methyl-4ʹ-amino-diphenylamin-6-sulfonsäure-­Na-Salz 22. 2,4-Dinitro-2ʹ-methyl-4ʹ-aminodiphenylamine-6-sulfonic acid Na salt

Die Herstellung erfolgte analog Beispiel 18. Anstatt p-Phe­nylendiamin wurden 3,75 g p-Toluylendiaminsulfat (0,017 Mol) eingesetzt. Rotbraune Kristalle.
Schmelzpunkt oberhalb 305°CThe preparation was carried out analogously to Example 18. Instead of p-phenylenediamine, 3.75 g of p-toluenediamine sulfate (0.017 Mol) used. Red-brown crystals.
Melting point above 305 ° C

23. 2,4-Dinitro-4ʹ-N,N-bis-(β-hydroxyethyl)-amino-diphenylamin-­6-sulfonsäure-Na-Salz 23. 2,4-Dinitro-4ʹ-N, N-bis- (β-hydroxyethyl) amino-diphenylamine-6-sulfonic acid Na salt

Die Herstellung erfolgte analog Beispiel 18. Anstatt p-Phe­nylendiamin wurden 4,6 g N,N-bis-(β-hydroxyethyl)-p-­phenylendiamin (0,017 Mol) eingesetzt. Schwarze Kristalle.
Schmelzpunkt 174°CThe preparation was carried out analogously to Example 18. Instead of p-phenylenediamine, 4.6 g of N, N-bis- (β-hydroxyethyl) -p-phenylenediamine (0.017 mol) were used. Black crystals.
Melting point 174 ° C

Folgende literaturbekannte Verbindungen wurden zusätzlich in die Haarfärbeversuche einbezogen:The following compounds known from the literature were also included in the hair dye tests:

24. 2,4-Dinitrodiphenylamin-6-sulfonsäure-Na-Salz 24. 2,4-Dinitrodiphenylamine-6-sulfonic acid Na salt

(Ann. 366, 83 (1909))(Ann. 366 , 83 (1909))

25. 2,6-Dinitro-diphenylamin-4-carbonsäure 25. 2,6-Dinitro-diphenylamine-4-carboxylic acid

(Am. Chem. J. 19, 18 (1897))(Am. Chem. J. 19 , 18 (1897))

26. 2,6-Dinitro-diphenylamin-4-sulfonsäure 26. 2,6-Dinitro-diphenylamine-4-sulfonic acid

(Ann. 366, 106 (1909))(Ann. 366 , 106 (1909))

HaarfärbeversucheHair dye attempts

Es wurden Haarfärbecremes der folgenden Zusammensetzung hergestellt:

Figure imgb0004
Hair dye creams of the following composition were produced:
Figure imgb0004

Die Bestandteile wurden der Reihe nach miteinander vermischt. Nach Zugabe der direktziehenden Farbstoffe wurde mit konzen­trierter Ammoniak-Lösung der pH-Wert der Emulsion auf 9,5 ein­gestellt, dann wurde mit Wasser auf 100 g aufgefüllt.The ingredients were mixed together in order. After the direct dyes had been added, the pH of the emulsion was adjusted to 9.5 with concentrated ammonia solution, and the mixture was then made up to 100 g with water.

Die Färbecreme wurde auf ca. 5 cm lange Strähnen standardisier­ten, zu 90% ergrauten, aber nicht besonders vorbehandelten Menschenhaars aufgetragen und dort 30 Minuten bei 27°C be­lassen. Nach Beendigung des Färbeprozesses wurde das Haar ge­spült, mit einem üblichen Haarwaschmittel ausgewaschen und an­schließend getrocknet.The coloring cream was applied to approx. 5 cm long strands of standardized, 90% gray, but not specially pretreated human hair and left there at 27 ° C for 30 minutes. After the dyeing process was completed, the hair was rinsed, washed out with a customary shampoo and then dried.

Als direktziehende Haarfarbstoffe wurden die Verbindungen gemäß Beispiel 1 bis 26 eingesetzt.The compounds according to Examples 1 to 26 were used as direct hair dyes.

Das Ergebnis der Färbeversuche ist der Tabelle I zu entnehmen.

Figure imgb0005
The result of the dyeing tests is shown in Table I.
Figure imgb0005

Claims (3)

1. The use of compounds corresponding to formula I
Figure imgb0007
 in which one of the groups R¹ or R² is a nitro group and the other is an -S0₃H or -COOH- group and the groups R³ to R⁵ independently of one another represent hydrogen, C₁-C₄ alkyl groups or one of the groups R³ to R⁵ is a hydroxy group or an amino group of the formula NR⁶R⁷, where R⁶ and R⁷ repre­sent hydrogen, C₁-C₄ alkyl groups or C₂-C₄ hydroxyalkyl groups, and the other two represent hydrogen or C₁-C₄ alkyl groups or one represents hydrogen or a C₁-C₄ alkyl group and the other a hydroxymethyl group, a C₁-C₄ alkoxy group or chlorine,
or water-soluble salts thereof as substantive hair dyes for the production of hair dyeing preparations.
2. The use claimed in claim 1, characterized in that the group R³ is a hydroxyl group or an amino group -NR⁶R⁷, where R⁶ and R⁷ are as defined in Claim 1.
3. Hair-dyeing preparations containing substantive hair dyes in a cosmetic carrier based on typical constituents of such cosmetic preparations, characterized in that compounds of formula I according to claim 1 or 2 are present as the substantive dyes in a quantity of from 0.01 to 5% by weight, based on the hair-dyeing preparation as a whole.
EP86114302A 1985-10-24 1986-10-16 Direct hair dyeing composition containing derivatives of nitrodiphenyl amine Expired - Lifetime EP0220614B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86114302T ATE60221T1 (en) 1985-10-24 1986-10-16 HAIR DYE CONTAINING DIRECT DYE NITRODIPHENYLAMINE DERIVATIVES.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3537765 1985-10-24
DE19853537765 DE3537765A1 (en) 1985-10-24 1985-10-24 HAIR DYE WITH DIRECT DRAWING NITRODIPHENYLAMINE DERIVATIVES

Publications (2)

Publication Number Publication Date
EP0220614A1 EP0220614A1 (en) 1987-05-06
EP0220614B1 true EP0220614B1 (en) 1991-01-23

Family

ID=6284296

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86114302A Expired - Lifetime EP0220614B1 (en) 1985-10-24 1986-10-16 Direct hair dyeing composition containing derivatives of nitrodiphenyl amine

Country Status (8)

Country Link
US (1) US4756715A (en)
EP (1) EP0220614B1 (en)
JP (1) JPS62103008A (en)
AT (1) ATE60221T1 (en)
DE (2) DE3537765A1 (en)
DK (1) DK504486A (en)
FI (1) FI864230A (en)
NO (1) NO168228C (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3706223A1 (en) * 1987-02-26 1988-09-08 Henkel Kgaa HAIR DYE WITH DIRECT DRAWING NITRODIPHENYLAMINE DERIVATIVES
JPH0794372B2 (en) * 1987-12-22 1995-10-11 ホーユー株式会社 Creamy hair dye first agent composition

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2687431A (en) * 1950-12-20 1954-08-24 Gen Aniline & Film Corp Process of preparing nitro phenylenediamines
DE1569808A1 (en) * 1965-12-19 1970-07-09 Oreal New nitro dyes and processes for their manufacture and use
CA1024071A (en) * 1972-08-09 1978-01-10 George Alperin Semi-permanent hair dye composition comprising a nitro-dye, a quaternary amine and certain n-oxyalkylated fatty acid amide
US3950127A (en) * 1972-12-26 1976-04-13 Clairol Incorporated Hair dye compositions containing nitrodiphenylamine dyes and method for dyeing hair therewith
FR2216271A1 (en) * 1973-02-01 1974-08-30 Ghinoin Gyogyszer Es Vegyeszet 3,5-Dintro-4-amine phenyl alkyl sulphones - herbicides
IT1081607B (en) * 1976-08-06 1985-05-21 Hoffmann La Roche BENZOIC ACID DERIVATIVES
GB1588215A (en) * 1976-08-06 1981-04-15 Roche Products Ltd Plant growth regulating and weed killing agents containing anthranilic acid derivatives and certain anthranilic acid derivatives per se
DE2830497B1 (en) * 1978-07-12 1980-01-17 Schwarzkopf Gmbh Hans Process for dyeing human hair and means for carrying it out

Also Published As

Publication number Publication date
JPS62103008A (en) 1987-05-13
FI864230A0 (en) 1986-10-20
DK504486D0 (en) 1986-10-21
EP0220614A1 (en) 1987-05-06
ATE60221T1 (en) 1991-02-15
DE3677130D1 (en) 1991-02-28
US4756715A (en) 1988-07-12
NO864240D0 (en) 1986-10-23
NO864240L (en) 1987-04-27
NO168228C (en) 1992-01-29
NO168228B (en) 1991-10-21
DK504486A (en) 1987-04-25
DE3537765A1 (en) 1987-04-30
FI864230A (en) 1987-04-25

Similar Documents

Publication Publication Date Title
EP0613366B1 (en) 5,6-dihydroxyindoline as additives for hair-dyeing preparations
EP0039030B1 (en) Coupler components for oxidative hair dyes, their preparation and their use, and hair dyeing compositions containing them
EP0353531B1 (en) Hair dye
EP0170069B1 (en) Hair-dyeing compositions
DE10036748A1 (en) New 2-nitro-4-pyrrolyl-phenol and 4-nitro-6-chloro-2-pyrrolyl-phenol and known pyrrolyl-nitrophenols are used as direct dyes in colorants for keratin fibers etc., especially human hair
EP0063736A2 (en) Use of dihydroxy pyridines as couplers in oxidation hair dyes, and hair dyeing preparation
EP0002828B1 (en) Hair dyeing composition
EP0270972B1 (en) Oxidation hair dye compositions
EP0107027B1 (en) Hair dyeing compositions
EP0220614B1 (en) Direct hair dyeing composition containing derivatives of nitrodiphenyl amine
EP0220613B1 (en) Direct hair dyeing composition containing derivatives of nitrodiphenyl amine
EP0106089A1 (en) Hair dyeing composition
EP0226197A2 (en) Hair-dyeing compositions with direct-dyeing azomethine dyes
EP0280187B1 (en) Hair dyeing compositions with direct-dyeing nitro-diphenyl amine derivatives
EP0282749B1 (en) Hair dyeing compositions containing direct nitrodiphenylamine derivatives
DE2719424A1 (en) Oxidn. dye-based hair-dyeing compsn. - contg. di:amino-benzoxazole, di:amino-benzofuran or di:amino-benzoxazolinone derivs. as couplers
EP0280186B1 (en) Hair dyeing compositions with direct-dyeing nitrodiphenyl amine derivatives
EP0583324B1 (en) Hair-dyeing agent
EP0144740B1 (en) Hair dyeing composition
DE3045959C2 (en)
EP0348849B1 (en) Hairdying composition
DE2934329A1 (en) Oxidn. hair-dye compsns. - contg. bis:4-methoxy-5-aminophenyl-alkylene di:amine or salt deriv. as coupling component
EP0195363A2 (en) Hair-dyeing composition
DE3313905A1 (en) Novel 2,4-diaminophenol ethers as couplers for oxidative hair dyes
DE4011481A1 (en) OXIDATION FIBER

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR GB IT LI NL SE

17P Request for examination filed

Effective date: 19871104

17Q First examination report despatched

Effective date: 19891004

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB IT LI NL SE

REF Corresponds to:

Ref document number: 60221

Country of ref document: AT

Date of ref document: 19910215

Kind code of ref document: T

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REF Corresponds to:

Ref document number: 3677130

Country of ref document: DE

Date of ref document: 19910228

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19910923

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19910927

Year of fee payment: 6

Ref country code: DE

Payment date: 19910927

Year of fee payment: 6

Ref country code: AT

Payment date: 19910927

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19911004

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19911007

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19911031

Year of fee payment: 6

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19911211

Year of fee payment: 6

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19921016

Ref country code: AT

Effective date: 19921016

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19921017

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19921031

Ref country code: CH

Effective date: 19921031

Ref country code: BE

Effective date: 19921031

BERE Be: lapsed

Owner name: HENKEL K.G.A.A.

Effective date: 19921031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19930501

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19921016

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19930630

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19930701

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

EUG Se: european patent has lapsed

Ref document number: 86114302.2

Effective date: 19930510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051016